Preparation of hydrogen peroxide, C1 to C4-monopercarboxylic acid and C4- to C18-dipercarboxylic acid complexes in a fluidized-bed process

ABSTRACT

A fluidized-bed process for preparing hydrogen peroxide, C 1  -C 4  -monopercarboxylic acids and C 4  -C 18  -dipercarboxylic acid complexes in which a solution of hydrogen peroxide, a C 1  -C 4  -monopercarboxylic acid, a C 4  -C 18  -dipercarboxylic acid or a mixture thereof in water or carboxylic acids is applied to a pulverulent or pregranulated matrix and fluidized-bed drying takes place.

The present invention relates to an improved process for preparinghydrogen peroxide, C₁ - to C₄ -monopercarboxylic acid and C₄ - to C₁₈-dipercarboxylic acid complexes in a fluidized-bed process by applying asolution of hydrogen peroxide, C₁ - to C₄ -monopercarboxylic acids, C₄ -to C₁₈ -dipercarboxylic acids or a mixture thereof in water orcarboxylic acids to a pulverulent or pregranulated matrix in or outsidethe fluidized bed and simultaneous or subsequent fluidized-bed drying.

Since some of the complexes prepared by the process of the invention arenew, the invention further relates to these novel substances.

U.S. Pat. No. 3,376,110 (1) and U.S. Pat. No. 3,480,557 (2) discloseswater-insoluble (crosslinked) or water-soluble (uncrosslinked) hydrogenperoxide complexes of polymeric N-vinylheterocycles such aspoly-N-vinylpyrrolidone and also poly-N-vinyl-2-caprolactam. Thesecomplexes can be prepared by evaporation of an aqueous suspension ofpolymer and hydrogen peroxide.

U.S. Pat. No. 5,077,047 (3) describes a process for preparingfree-flowing pulverulent hydrogen peroxide/poly-N-vinylpyrrolidonecomplexes in a fluidized-bed process. The drying of the product formedcan be carried out in the fluidized bed simultaneously or in adownstream step.

U.S. Pat. No. 5,190,749 (4) discloses that the fluidized-bed processfrom (3) can also be used for preparing hydrogen peroxide complexes fromcopolymers of N-vinylpyrrolidone with quaternized ammonium monomers.

Hydrogen peroxide/urea complexes can also be prepared in a fluidized-bedprocess according to DE-A 34 44 552 (5), with the drying of the reactionproduct being able to be carried out in one process step in the sameapparatus or in a downstream drying step.

WO 92/17158 (7) discloses that a hydroxyalkylcellulose such ashydroxyethylcellulose can be added as foam pore enlarger to the hydrogenperoxide/poly-N-vinylpyrrolidone complexes during their preparation in afluidized bed.

It is an object of the present invention to provide an improvedpreparation process for such hydrogen peroxide complexes, since thepreparation processes described in the prior art are still notsufficiently efficient and economical. Furthermore, the known hydrogenperoxide/polymer complexes are deficient with regard to their propertiesduring preparation and during use, so that there is also a need for newimproved complexes of per-compounds.

We have found that this object is achieved by the process defined in theintroduction for preparing hydrogen peroxide, C₁ - to C₄-monopercarboxylic acid and C₄ - to C₁₈ -dipercarboxylic acid complexesin a fluidized-bed process, wherein the matrix used is

A) an N-vinylcaprolactam homopolymer,

B) an N-vinylcaprolactam copolymer with N-vinylpyrrolidone,N-vinylimidazole, acryl- or methacrylamidopropyl-3-sulfonic acid,acrylic or methacrylic acid or a mixture thereof as comonomer in aweight ratio of N-vinylcaprolactam to comonomer of from 20:1 to 1:20,

C) an N-vinylpyrrolidone copolymer with N-vinylimidazole, acrylic ormethacrylic acid or a mixture thereof as comonomer in a weight ratio ofN-vinylpyrrolidone to comonomer of from 20:1 to 1:20,

D) an N-vinylimidazole homopolymer which can be substituted on theheterocyclic ring by up to three C₁ - to C₄ -alkyl radicals and can beN-quaternized by C₁ - to C₄ -alkyl,

E) a mixture of monosaccharides, oligosaccharides, polysaccharides orderivatives thereof with the polymers A to D in a weight ratio of from1:99 to 90:10,

F) a mixture of monosaccharides, oligosaccharides, starches, starchdegradation products or derivatives thereof with N-vinylpyrrolidonehomopolymers in a weight ratio of from 1:99 to 90:10,

G) a mixture of trehalose, saccharose, glucose, α-, β- orγ-cyclodextrins or derivatives of these cyclodextrins or a mixturethereof with the polymers A to D or with N-vinylpyrrolidone homopolymersin a weight ratio of from 1:99 to 100:0 or

H) in the case of C₁ - to C₄ -monopercarboxylic acid and C₄ - to C₁₈-dipercarboxylic acid complexes, N-vinylpyrrolidone homopolymers.

For the purposes of the present invention, N-vinylcaprolactam isN-vinyl-ε-caprolactam (N-vinyl-2-caprolactam), and N-vinylpyrrolidone isN-vinyl-2-pyrrolidone.

Preferred copolymers B based on N-vinylcaprolactam areN-vinylcaprolactam/N-vinylpyrrolidone bipolymers,N-vinylcaprolactam/N-vinylimidazole bipolymers,N-vinylcaprolactam/N-vinylpyrrolidone/N-vinylimidazole terpolymers,N-vinylcaprolactam/acrylic or methacrylic acid bipolymers andN-vinylcaprolactam/acryl- or methacrylamidopropyl-3-sulfonic acidbipolymers. Any carboxylic acid or sulfonic acid groups present can bepartially or completely present as salts, e.g. as sodium, potassium,ammonium or substituted ammonium salts.

Furthermore, the polymers B and also the homopolymers A can beuncrosslinked or crosslinked. The degree of water solubility can beadjusted by crosslinking. The process of the invention can be carriedout particularly well using crosslinkedN-vinylcaprolactam/N-vinylpyrrolidone copolymers ("Popcorn" polymers) asdescribed in DE-C 24 37 629 (6). Crosslinking is best carried out byadding divinylethylene urea as crosslinking monomer in amounts of from0.5 to 10% by weight, preferably from 2 to 8% by weight, based on theweight of the monomers specified under B, during the polymerization.However, it is also possible to effect crosslinking by addition ofcatalysts such as alkali metal hydrides or borohydrides.

In the copolymers B, the weight ratio of N-vinylcaprolactam to thecomonomers N-vinylpyrrolidone, N-vinylimidazole, acryl- ormethacrylamidopropyl-3-sulfonic acid and/or acrylic or methacrylic acidis from 20:1 to 1:20, preferably from 15:1 to 1:4, in particular from10:1 to 1:1.

Preferred copolymers C based on N-vinylpyrrolidone areN-vinylpyrrolidone/N-vinylimidazole bipolymers andN-vinylpyrrolidone/acrylic acid or methacrylic acid bipolymers. Thecopolymers C can be uncrosslinked or crosslinked in a manner similar tothe polymers A and B.

In the copolymers C, the weight ratio of N-vinylpyrrolidone to thecomonomers N-vinylimidazole and/or acrylic or methacrylic acid is from20:1 to 1:20, preferably from 4:1 to 1:10, in particular from 1:1 to1:8.

Suitable N-vinylimidazole homopolymers D substituted by up to three,preferably by up to two, particularly preferably by one, C₁ - to C₄-alkyl radical are, for example, those of 2-methyl-, 4-methyl- or5-methylimidazole.

Suitable N-vinyl-N'-C₁ - to C₄ -alkylimidazolium homopolymers D are, forexample, N-vinyl-N'-methyl-, N-vinyl-N'-ethyl- orN-vinyl-N'-butylimidazolium homopolymers. Counterions to the cationicquaternary nitrogen atoms can be, for example, chloride, bromide ormethosulfate. The quaternization of the nitrogen atoms can have beencarried out prior to or after the polymerization. The homopolymers D canbe uncrosslinked or crosslinked in a manner similar to the polymers A toC.

The mixtures E and F of the polymers A to D or N-vinylpyrrolidonehomopolymers with carbohydrates or carbohydrate derivatives showparticularly good use properties, in particular, the dissolutionproperties of the final hydrogen peroxide or percarboxylic acidcomplexes are optimum. The weight ratio of the carbohydrates orcarbohydrate derivatives to the specified polymers is from 1:99 to90:10, preferably from 10:90 to 70:30, in particular from 20:80 to50:50.

The carbohydrate component is a natural product based onmonosaccharides, oligosaccharides, polysaccharides or their derivatives.From an economic point of view, the preparation preferably usesstarches, thermally and/or mechanically treated starches, oxidatively,hydrolytically or enzymatically degraded starches, oxidizedhydrolytically degraded starches or oxidized enzymatically degradedstarches, or chemically modified starches or chemically modifiedmonosaccharides or oligosaccharides. In principle, all starches aresuitable. The starches are virtually insoluble in water and can beconverted into a water-soluble form in a known manner by thermal and/ormechanical treatment or by enzymatic or acid-catalyzed degradation.

Examples which may be mentioned of starch degradation products which areobtainable either by oxidative, hydrolytic or enzymatic degradation ofstarch are the following compounds: dextrins such as white and yellowdextrins, maltodextrins, glucose syrup, maltose syrup, hydrolysateshaving a high content of D-glucose or maltose and D-glucose or theirisomerization product fructose.

Other saccharides which are suitable as component B are monosaccharidesand oligosaccharides such as galactose, mannose, ribose, saccharose,raffinose, lactose, trehalose and degradation products of cellulose, forexample cellubiose and their oligomers. The cyclodextrins of variousring size and their derivatives are also suitable.

Preference is given to unreduced saccharides.

If, as described under G, the carbohydrate component used is trehalose,saccharose, glucose, α-, β- or γ-cyclodextrins or derivatives of thesecyclodextrins or mixtures thereof, their proportion in the matrixmaterial can be increased to 100% by weight, ie. the per-compound caneven be applied to the pure carbohydrate in the process of theinvention. The weight ratio of these carbohydrate components to thepolymers A to D or N-vinylpyrrolidone homopolymers can thus be, goingbeyond E or F, from 1:99 to 100:0, preferably from 10:90 to 100:0, inparticular from 20:80 to 100:0.

The Fikentscher K values as a measure of the molecular weight of thepolymers A to D and H used are mostly from 10 to 90, in particular from17 to 60, measured under the customary conditions therefor, eg. in H₂ Oat room temperature.

In the preparation of the polymers A to D and H or of the polymersforming the basis of the mixtures E to G, it is possible to add smallamounts of further customary copolymerizable monomers to slightly modifythe properties of these polymers for the purposes of the presentinvention.

Suitable C₁ - to C₄ -monopercarboxylic acids (monoperoxycarboxylicacids) are primarily C₂ - to C₄ -monopercarboxylic acids, in particularperacetic acid, perpropionic acid, perbutyric acid and isoperbutyricacid. Performic acid can also be used if the necessary safetyprecautions are taken, bearing in mind the instability of this compound.

Suitable C₄ - to C₁₈ -dipercarboxylic acids (diperoxycarboxylic acids)are primarily C₈ - to C₁₄ -dipercarboxylic acids, in particular1,12-diperoxydodecanoic acid and 1,14-diperoxytetradecanoic acid.

Use is made of solutions of the per-compounds having a per-compoundcontent of normally from 1 to 80% by weight, in particular from 3 to 50%by weight, in the case of hydrogen peroxide or of from 0.5 to 30% byweight, in particular from 1 to 15% by weight, in the case of thepercarboxylic acids, in water, in carboxylic acids, usually thecarboxylic acids on which the per-compound is based, or mixtures ofwater and carboxylic acids. When using percarboxylic acids, aqueoussolutions usually contain additional hydrogen peroxide.

The application of the aqueous solutions of the per-compounds to thepulverulent or pregranulated matrix A to H is preferably carried out ina fluidized bed, but it can also be carried out in an upstream step. Theapplication is advantageously carried out by spraying of the solutionsby means of nozzles.

The fluidized-bed drying to remove the water introduced mainly by theaqueous solutions of the per-compounds is preferably carried outsimultaneously with the application of the per-compounds to the matrix,but can also be carried out in a separate step in the same or in adownstream apparatus. To obtain a free-flowing, ie. pourable, powder ofthe hydrogen peroxide or percarboxylic acid complexes, the water contentshould be less than 5% by weight after drying; this avoids blocking.

The temperature during application of the aqueous solutions of theper-compounds is usually from 25° to 80° C. for the inlet air and from25° to 70° C. for the outlet air; for both inlet and outlet air,preference is given to a temperature range of from 30° to 60° C. in eachcase, in particular from 35° to 55° C. Further details for carrying outsuch a fluidized-bed process with regard to theoretical fundamentals,reactor types and industrial embodiments can be found in UllmannsEncyklopadie der technischen Chemie, 4th edition, volume 3 (1973), pp.433-460 and pp. 480-493.

The hydrogen peroxide and percarboxylic acid complexes prepared by theprocess of the invention have per-compound contents of from 1 to 35% byweight, preferably from 3 to 30% by weight, in particular from 5 to 25%by weight, based on the solids content in the product obtained.

The hydrogen peroxide and percarboxylic acid complexes described can, inprinciple, also be obtained without problems and with the same yields,purities and per-compound contents by precipitation from aqueoussolutions of the polymers A to D and H by addition of aqueous solutionsof the per-compounds, filtering or decanting off and drying, but thismethod cannot be satisfactorily transferred to a large scale.

The present invention also provides a hydrogen peroxide, C₁ - to C₄-monopercarboxylic acid or C₄ - to C₁₈ -dipercarboxylic acid complex ofan N-vinylcaprolactam copolymer with N-vinylpyrrolidone,N-vinylimidazole, acryl- or methacrylamidopropyl-3-sulfonic acid,acrylic or methacrylic acid or a mixture thereof as comonomer in aweight ratio of N-vinylcaprolactam to comonomer of from 20:1 to 1:20,containing from 1 to 35% by weight of per-compounds.

The present invention further provides a hydrogen peroxide, C₁ - to C₄-monopercarboxylic acid or C₄ - to C₁₈ -dipercarboxylic acid complex ofa N-vinylpyrrolidone copolymer with N-vinylimidazole, acrylic ormethacrylic acid or a mixture thereof as comonomer in a weight ratio ofN-vinylpyrrolidone to comonomer of from 20:1 to 1:20, containing from 1to 35% by weight of per-compounds.

The present invention further provides a hydrogen peroxide, C₁ - to C₄-monopercarboxylic acid or C₄ - to C₁₈ -dipercarboxylic acid complex ofan N-vinylimidazole homopolymer which can be substituted on theheterocyclic ring by up to three C₁ - to C₄ -alkyl radicals and can beN-quaternized by C₁ - to C₄ -alkyl, containing from 1 to 35% by weightof per-compounds.

The present invention further provides a hydrogen peroxide, C₁ - to C₄-monopercarboxylic acid or C₄ - to C₁₈ -dipercarboxylic acid complex ofa mixture of monosaccharides, oligosaccharides, polysaccharides orderivatives thereof with

(a) an N-vinylcaprolactam homopolymer,

(b) an N-vinylcaprolactam copolymer with N-vinylpyrrolidone,N-vinylimidazole, acryl- or methacrylamidopropyl-3-sulfonic acid,acrylic or methacrylic acid or a mixture thereof as comonomer in aweight ratio of N-vinylcaprolactam to comonomer of from 20:1 to 1:20,

(c) an N-vinylpyrrolidone copolymer with N-vinylimidazole, acrylic ormethacrylic acid or a mixture thereof as comonomer in a weight ratio ofN-vinylpyrrolidone to comonomer of from 20:1 to 1:20 or

(d) an N-vinylimidazole homopolymer which can be substituted on theheterocyclic ring by up to three C₁ - to C₄ -alkyl radicals and can beN-quaternized by C₁ - to C₄ -alkyl,

in a weight ratio of from 1:99 to 90:10, containing from 1 to 35% byweight of per-compounds.

The present invention further provides a hydrogen peroxide, C₁ - to C₄-monopercarboxylic acid or C₄ - to C₁₈ -dipercarboxylic acid complex ofa mixture of monosaccharides, oligosaccharides, starches, starchdegradation products or derivatives thereof with an N-vinylpyrrolidonehomopolymer in a weight ratio of from 1:99 to 90:10, containing from 1to 35% by weight of per-compounds.

The present invention further provides a hydrogen peroxide, C₁ - to C₄-monopercarboxylic acid or C₄ - to C₁₈ -dipercarboxylic acid complex ofa mixture of trehalose, saccharose, glucose, α-, β- or γ-cyclodextrinsor mixtures of these cyclodextrins or a mixture thereof with

(a) an N-vinylcaprolactam homopolymer,

(b) an N-vinylcaprolactam copolymer with N-vinylpyrrolidone,N-vinylimidazole, acryl- or methacrylamidopropyl-3-sulfonic acid,acrylic or methacrylic acid or a mixture thereof as comonomer in aweight ratio of N-vinylcaprolactam to comonomer of from 20:1 to 1:20,

(c) an N-vinylpyrrolidone copolymer with N-vinylimidazole, acrylic ormethacrylic acid or a mixture thereof as comonomer in a weight ratio ofN-vinylpyrrolidone to comonomer of from 20:1 to 1:20,

(d) an N-vinylimidazole homopolymer which can be substituted on theheterocyclic ring by up to three C₁ - to C₄ -alkyl radicals and can beN-quaternized by C₁ - to C₄ -alkyl, or

(e) an N-vinylpyrrolidone homopolymer

in a weight ratio of from 1:99 to 100:0, containing from 1 to 35% byweight of per-compounds.

The present invention further provides a C₁ - to C₄ -monopercarboxylicacid or C₄ - to C₁₈ -dipercarboxylic acid complex of anN-vinylpyrrolidone homopolymer, containing from 1 to 35% by weight ofper-compounds.

Using the process of the invention it is possible to obtain hydrogenperoxide and percarboxylic acid complexes of various hydrophilicity as afunction of the proportion of hydrophobic comonomer such asN-vinylcaprolactam in an efficient and economical manner. Particularlyin the case of matrix material based on N-vinylcaprolactam, thefluidized-bed drying proceeds more quickly than in the case ofN-vinylpyrrolidone homopolymers, since the former is less hygroscopic;such powders are free flowing. In warm storage of the complexes ofper-compounds prepared by means of the matrix materials A to H, theproducts prepared according to the invention generally achieve betterresults in stability testing (for example by means of differentialthermogravimetry) than the products of the prior art.

Differential thermogravimetry (heating rate of 2° K/min, 30°-400° C.)gives an onset temperature of 110° C. and a peak maximum temperature of165° C. for an uncrosslinked polyvinylcaprolactam/H₂ O₂ complexcontaining 4.8% by weight of H₂ O₂. In contrast, a commercialuncrosslinked polyvinylpyrrolidone/H₂ O₂ complex containing 18% byweight of H₂ O₂ has an onset temperature of only 60° C. and a peakmaximum temperature of 155° C.

Hydrogen peroxide and percarboxylic acid complexes prepared by theprocess of the invention can be used, for example, as a disinfectant orpreservative, in particular in toothpastes, in treatment of acne, aswound dressings, in cosmetics, eg. in hair cosmetics (hair coloring,hair bleaching) and in depilation, or as solid components for chemicalreactions such as polymerizations or oxidations, furthermore asdetergent additive or as auxiliary in bleaching of textiles and paper,and also as constituents of filter systems, eg. for water treatment orin medicine for blood treatment, into which the complexes described withcrosslinked polymers can be incorporated or to which they can beapplied.

EXAMPLES

In testing as disinfectant according to the guidelines of the DeutscheGesellschaft fur Hygiene und Mikrobiologie (DGHM), the minimuminhibition concentration was determined. In this test, a commercialuncrosslinked polyvinylpyrrolidone/H₂ O₂ complex (20.2% by weight of H₂O₂) gave a value of 5.0%, while an uncrosslinked polyvinylcaprolactam/H₂O₂ complex (10.9% by weight of H₂ O₂) gave a value of 5.0% and an H₂ O₂complex with a mixture of an uncrosslinked polyvinylpyrrolidone andmaltodextrin (as described in Example 4 or 5 below) containing 10.1% byweight of H₂ O₂ gave a value of 2.5%.

Testing was here carried out in accordance with the Richtlinien fur diePrufung und Bewertung chemischer Desinfektionsverfahren (version: Jan.1, 1981) of the DGHM. Evaluation is carried out after incubation for 72hours at 36° C. Dilution is carried out using water of standardizedhardness without further auxiliaries (surfactants). The adjustment ofthe pH to 7.2 is carried out using 0.1 mol/l NaOH or using 0.1 mol/lHCl. The test concentration steps were in accordance with the followingdilution steps (all values in % by volume):

100, 75, 50, 25, 20, 15, 10, 7.5, 5.0, 4.0, 3.0, 2.5, 2.0, 1.5, 1.00,0.75, 0.50, 0.25, 0.10, 0.05, 0.025, 0.0125, 0.00625 (and so forth in ageometric series, ie. the concentration reduced by a factor of 0.5 eachtime).

Preparation in a fluidized-bed process

Fluidized-bed granulation was carried out in a granulation cylinderwhich was bounded at the bottom by a perforated plate with attachedsieve (mesh size 10-500 μm) and at the top by 4 filter sacks which wereblown clean every 15 seconds by compressed air. A two-fluid nozzlehaving an extended liquid inlet was located 28 cm above the sieve plate.The metering in of the hydrogen peroxide or peracetic acid solution wascarried out by means of a peristaltic pump. The process air was alsoable to be replaced by nitrogen. The air throughput was about 120 m³ /hand was able to be roughly regulated by means of an outlet air flap.During drying, the air flow was increased to 150 m³ /h. The possibleinput amount of solid polymer powder for this apparatus was from 100 to4000 g. The mean particle size was able to be adjusted by means of thetwo parameters feed rate and air pressure of the spray nozzle.

Example 1

150 g of N-vinylcaprolactam homopolymer were initially charged in thefluidized bed and sprayed at about 50° C. with a 30% strength by weighthydrogen peroxide solution. At intervals in the portion-wise addition ofthe hydrogen peroxide solution, the powder was completely dried in theair stream. Further drying could be carried out after the process wascomplete, but was not absolutely necessary.

Table 1 shows the amount of H₂ O₂ solution applied and the H₂ O₂ contentfound in the solid product:

                  TABLE 1                                                         ______________________________________                                        H.sub.2 O.sub.2 solution  g!                                                                   H.sub.2 O.sub.2 content  % by weight!                        ______________________________________                                        10               1.2                                                          20               2.82                                                         30               4.34                                                         40               5.71                                                         50               6.68                                                         60               5.1                                                          70               8.72                                                         80               9.98                                                         90               9.63                                                         100              10.9                                                         ______________________________________                                    

Example 2

N-vinylpyrrolidone/N-vinylimidazole "Popcorn" polymer (weight ratio 1:8)was initially charged as powder (154 g), sprayed at an inlet airtemperature of 50° C. with a 30% strength by weight hydrogen peroxidesolution and dried in a similar manner to Example 1.

Table 2 shows the amount of H₂ O₂ solution applied and the H₂ O₂ contentfound in the solid product:

                  TABLE 2                                                         ______________________________________                                        H.sub.2 O.sub.2 solution  g!                                                                   H.sub.2 O.sub.2 content  % by weight!                        ______________________________________                                        10               2.75                                                         20               5.59                                                         30               8.22                                                         40               10.4                                                         50               13.2                                                         60               15.4                                                         70               17.1                                                         80               18.7                                                         90               19.5                                                         100              20.5                                                         ______________________________________                                    

Example 3

Normally polymerized N-vinylpyrrolidone/N-vinylimidazole copolymer(weight ratio 1:8) was likewise used as powder and reacted under thesame conditions as in Example 1. The final content of hydrogen peroxidewas 19.5% by weight.

Example 4

75 g of N-vinylpyrrolidone homopolymer and 25 g of maltodextrin wereinitially charged as matrix material. The experimental conditions wereas in Example 1.

Table 3 shows the amount of H₂ O₂ solution applied and the H₂ O₂ contentfound in the solid product:

                  TABLE 3                                                         ______________________________________                                        H.sub.2 O.sub.2 solution  g!                                                                   H.sub.2 O.sub.2 content  % by weight!                        ______________________________________                                        10               2.51                                                         20               5.55                                                         30               7.72                                                         40               8.84                                                         50               10.6                                                         ______________________________________                                    

Example 5

65 g of N-vinylpyrrolidone homopolymer and 35 g of maltodextrin wereinitially charged as matrix material. The experimental conditions wereas in Example 1.

Table 4 shows the amount of H₂ O₂ solution applied and the H₂ O₂ contentfound in the solid product:

                  TABLE 4                                                         ______________________________________                                        H.sub.2 O.sub.2 solution  g!                                                                   H.sub.2 O.sub.2 content  % by weight!                        ______________________________________                                        10               1.46                                                         20               4.28                                                         30               8.83                                                         40               10.8                                                         50               11.4                                                         ______________________________________                                    

Example 6

N-vinylpyrrolidone/N-vinylcaprolactam copolymer having a weight ratio of1:9 was initially charged (100 g). The experimental conditions were asin Example 1.

Table 5 shows the amount of H₂ O₂ solution applied and the H₂ O₂ contentfound in the solid product:

                  TABLE 5                                                         ______________________________________                                        H.sub.2 O.sub.2 solution  g!                                                                   H.sub.2 O.sub.2 content  % by weight!                        ______________________________________                                        10               2.7                                                          20               5.8                                                          30               8.4                                                          40               11.2                                                         50               13.3                                                         60               15.7                                                         70               16.7                                                         80               18.4                                                         90               19.4                                                         100              21.7                                                         ______________________________________                                    

Example 7

Use of an N-vinylpyrrolidone/N-vinylcaprolactam/N-vinylimidazoleterpolymer having a weight ratio of 5:1:2 (100 g) and addition of 100 gof H₂ O₂ enabled a final content of 20.3% by weight of H₂ O₂ to beachieved.

Example 8

Use of a cross-linked N-vinylcaprolactam/N-vinylpyrrolidone copolymerhaving a weight ratio of 1:1 (100 g) enabled a final content of 32% byweight of H₂ O₂ to be achieved.

Example 9

100 g of N-vinylpyrrolidone homopolymer (K value: 30, measured in H₂ Oat 25° C.) were treated with 5% strength by weight aqueous peraceticacid solution containing 26-27% by weight of hydrogen peroxide, at aninlet air temperature of 40° C. and an outlet air temperature of 35° C.,and dried in a similar manner to Example 1.

Table 6 shows the amount of peracid solution applied and the H₂ O₂/peracid contents found in the solid product:

                  TABLE 6                                                         ______________________________________                                                         H.sub.2 O.sub.2 /peracid content  % by                       Peracid solution  g!                                                                           weight!                                                      ______________________________________                                        10               1.7/0.7                                                      20               4.0/1.2                                                      30               6.7/1.5                                                      40               7.7/1.7                                                      ______________________________________                                    

After 4 hours at 70° C., the complex lost about 10% of the hydrogenperoxide content and 12% of the peracetic acid content.

Example 10

An N-vinylpyrrolidone/N-vinylcaprolactam copolymer having a weight ratioof 1:9 (100 g) was treated in a similar manner to Example 9.

Table 7 shows the amount of peracid solution applied and the H₂ O₂/peracid contents found in the solid product:

                  TABLE 7                                                         ______________________________________                                                         H.sub.2 O.sub.2 /Peracid content  % by                       Peracid solution  g!                                                                           weight!                                                      ______________________________________                                        10               1.9/0.5                                                      20               4.2/0.9                                                      30               6.9/1.5                                                      40               8.5/1.9                                                      ______________________________________                                    

Example 11

100 g of crosslinked N-vinylpyrrolidone homopolymer were treated in asimilar manner to Example 9.

Table 8 shows the amount of peracid solution applied and the H₂ O₂/peracid contents found in the solid product:

                  TABLE 8                                                         ______________________________________                                                         H.sub.2 O.sub.2 /Peracid content  % by                       Peracid solution  g!                                                                           weight!                                                      ______________________________________                                        10               1.8/0.4                                                      20               4.1/0.8                                                      30               6.9/1.4                                                      40               7.9/1.8                                                      ______________________________________                                    

After 7 hours at 70° C., the complex lost about 11% of the hydrogenperoxide content and 10% of the peracetic acid content.

We claim:
 1. A process for preparing hydrogen peroxide, C₁ - to C₄-monopercarboxylic acid and C₄ - to C₁₈ -dipercarboxylic acid complexesin a fluidized-bed process which comprises: applying a solution ofhydrogen peroxide, C₁ - to C₄ -monopercarboxylic acids, C₄ - to C₁₈-dipercarboxylic acids or a mixture thereof in water or carboxylic acidsto a pulverulent or pregranulated matrix in or outside the fluidized bedand simultaneous or subsequent fluidized-bed drying, wherein the matrixused isA) an N-vinylcaprolactam homopolymer, B) an N-vinylcaprolactamcopolymer with N-vinylpyrrolidone, N-vinylimidazole, acryl- ormethacrylamido-propyl-3-sulfonic acid, acrylic or methacrylic acid or amixture thereof as comonomer in a weight ratio of N-vinylcaprolactam tocomonomer of from 20:1 to 1:20, C) an N-vinylpyrrolidone copolymer withN-vinylimidazole, acrylic or methacrylic acid or a mixture thereof ascomonomer in a weight ratio of N-vinylpyrrolidone to comonomer of from20:1 to 1:20, D) an N-vinylimidazole homopolymer which can besubstituted on the heterocyclic ring by up to three C₁ - to C₄ -alkylradicals and can be N-quaternized by C₁ - to C₄ -alkyl radicals, E) amixture of monosaccharides, oligosaccharides or polysaccharides with oneor more of the polymers A to D in a weight ratio of from 1:99 to 90:10,F) a mixture of monosaccharides, oligosaccharides, starches or starchdegradation products with N-vinylpyrrolidone homopolymers in a weightratio of from 1:99 to 90:10, G) a mixture of trehalose, saccharose,glucose, α-, β-, or γ-cyclodextrins or a mixture thereof with one ormore of the polymers A to D or with N-vinylpyrrolidone homopolymers in aweight ratio of from 1:99 to 100:0 or H) in the case of C₁ - to C₄-monopercarboxylic acid and C₄ - to C₁₈ -dipercarboxylic acid complexes,N-vinylpyrrolidone homopolymers.
 2. A hydrogen peroxide, C₁ - to C₄-monopercarboxylic acid or C₄ - to C₁₈ -dipercarboxylic acid complex ofan N-vinylcaprolactam copolymer with N-vinylpyrrolidone,N-vinylimidazole, acryl- or methacrylamidopropyl-3-sulfonic acid,acrylic or methacrylic acid or a mixture thereof as comonomer in aweight ratio of N-vinylcaprolactam to comonomer of from 20:1 to 1:20,containing from 1 to 35% by weight of per-compounds.
 3. A hydrogenperoxide, C₁ - to C₄ -monopercarboxylic acid or C₄ - to C₁₈-dipercarboxylic acid complex of an N-vinylpyrrolidone copolymer withN-vinylimidazole, acrylic or methacrylic acid or a mixture thereof ascomonomer in a weight ratio of N-vinylpyrrolidone to comonomer of from20:1 to 1:20, containing from 1 to 35% by weight of per-compounds.
 4. AC₁ - to C₄ -monopercarboxylic acid or C₄ - to C₁₈ -dipercarboxylic acidcomplex of an N-vinylimidazole homopolymer which can be substituted onthe heterocyclic ring by up to three C₁ - to C₄ -alkyl radicals and canbe N-quaternized by C₁ - to C₄ -alkyl radicals, containing from 1 to 35%by weight of per-compounds.
 5. A hydrogen peroxide, C₁ - to C₄-monopercarboxylic acid or C₄ - to C₁₈ -dipercarboxylic acid complex ofa mixture of monosaccharides, oligosaccharides or polysaccharideswith(a) an N-vinylcaprolactam homopolymer, (b) an N-vinylcaprolactamcopolymer with N-vinylpyrrolidone, N-vinylimidazole, acryl ormethacrylamidopropyl-3-sulfonic acid, acrylic or methacrylic acid or amixture thereof as comonomer in a weight ratio of N-vinylcaprolactam tocomonomer of from 20:1 to 1:20, (c) an N-vinylpyrrolidone copolymer withN-vinylimidazole, acrylic or methacrylic acid or a mixture thereof ascomonomer in a weight ratio of N-vinylpyrrolidone to comonomer of from20:1 to 1:20 or (d) an N-vinylimidazole homopolymer which can besubstituted on the heterocyclic ring by up to three C₁ - to C₄ -alkylradicals and can be N-quaternized by C₁ - to C₄ -alkyl radicals,in aweight ratio of from 1:99 to 90:10, containing from 1 to 35% by weightof per-compounds.
 6. A hydrogen peroxide, C₁ - to C₄ -monopercarboxylicacid or C₄ - to C₁₈ -dipercarboxylic acid complex of a mixture ofmonosaccharides, oligosaccharides, starches or starch degradationproducts with an N-vinylpyrrolidone homopolymer in a weight ratio offrom 1:99 to 90:10, containing from 1 to 35% by weight of per-compounds.7. A hydrogen peroxide, C₁ - to C₄ -monopercarboxylic acid or C₄ - toC₁₈ -dipercarboxylic acid complex of a mixture of trehalose, saccharose,glucose, α-, β- or γ-cyclodextrins or a mixture thereof with(a) anN-vinylcaprolactam homopolymer, (b) an N-vinylcaprolactam copolymer withN-vinylpyrrolidone, N-vinylimidazole, acryl- ormethacrylamidopropyl-3-sulfonic acid, acrylic or methacrylic acid or amixture thereof as comonomer in a weight ratio of N-vinylcaprolactam tocomonomer of from 20:1 to 1:20, (c) an N-vinylpyrrolidone copolymer withN-vinylimidazole, acrylic or methacrylic acid or a mixture thereof ascomonomer in a weight ratio of N-vinylpyrrolidone to comonomer of from20:1 to 1:20, (d) an N-vinylimidazole homopolymer which can besubstituted on the heterocyclic ring by up to three C₁ - to C₄ -alkylradicals and can be N-quaternized by C₁ - to C₄ -alkyl radicals, or (e)an N-vinylpyrrolidone homopolymerin a weight ratio of from 1:99 to100:0, containing from 1 to 35% by weight of per-compounds.
 8. A C₁ - toC₄ -monopercarboxylic acid or C₄ - to C₁₈ -dipercarboxylic acid complexof an N-vinylpyrrolidone homopolymer, containing from 1 to 35% by weightof per-compounds.